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Search indexed NASA NTRS and DOE OSTI research on propulsion, heat transfer, battery materials and energy systems. Follow report and document links to the original sources.

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At least 91 records · Page 5
All sourcesNASA NTRSDOE OSTI
NASA NTRS2016

The Description and Validation of a Computationally-Efficient CH4-CO-OH (ECCOHv1.01) Chemistry Module for 3D Model Applications

We present the Efficient CH4-CO-OH (ECCOH) chemistry module that allows for the simulation of the methane, carbon monoxide, and hydroxyl radical (CH4-CO- OH) system, within a chemistry climate model, carbon cycle model, or Earth system model. The computational efficiency of the module allows many multi-decadal sensitivity simulations of the CH4-CO-OH system, which primarily determines the global atmospheric oxidizing capacity. This capability is important for capturing the nonlinear feedbacks of the CH4-CO-OH system and understanding the perturbations to methane, CO, and OH, and the concomitant impacts on climate. We implemented the ECCOH chemistry module in the NASA GEOS-5 atmospheric global circulation model (AGCM), performed multiple sensitivity simulations of the CH4-CO-OH system over 2 decades, and evaluated the model output with surface and satellite data sets of methane and CO. The favorable comparison of output from the ECCOH chemistry module (as configured in the GEOS- 5 AGCM) with observations demonstrates the fidelity of the module for use in scientific research.

carbon cycle model↗
NASA NTRS2013

Three Decades of Global Methane Sources and Sinks

Methane is an important greenhouse gas, responsible for about 20 of the warming induced by long-lived greenhouse gases since pre-industrial times. By reacting with hydroxyl radicals, methane reduces the oxidizing capacity of the atmosphere and generates ozone in the troposphere. Although most sources and sinks of methane have been identified, their relative contributions to atmospheric methane levels are highly uncertain. As such, the factors responsible for the observed stabilization of atmospheric methane levels in the early 2000s, and the renewed rise after 2006, remain unclear. Here, we construct decadal budgets for methane sources and sinks between 1980 and 2010, using a combination of atmospheric measurements and results from chemical transport models, ecosystem models, climate chemistry models and inventories of anthropogenic emissions. The resultant budgets suggest that data-driven approaches and ecosystem models overestimate total natural emissions. We build three contrasting emission scenarios which differ in fossil fuel and microbial emissions to explain the decadal variability in atmospheric methane levels detected, here and in previous studies, since 1985. Although uncertainties in emission trends do not allow definitive conclusions to be drawn, we show that the observed stabilization of methane levels between 1999 and 2006 can potentially be explained by decreasing-to-stable fossil fuel emissions, combined with stable-to-increasing microbial emissions. We show that a rise in natural wetland emissions and fossil fuel emissions probably accounts for the renewed increase in global methane levels after 2006, although the relative contribution of these two sources remains uncertain.

periodic variations↗
NASA NTRS2020

OMI Measurements of Bromine Monoxide and Implications for Missing Sources of Polar Bromine in GEOS-Chem

The OMI satellite instrument provides total column measurements of bromine monoxide (BrO) with daily global coverage. Reactive bromine compounds (Br and BrO) catalytically destroy ozone in both the stratosphere and troposphere. The current emission scheme of brominated source gases in the GEOS-Chem chemical transport model well represents the stratospheric burden of bromine. However, halogen research in GEOS-Chem has largely focused on the influence of halogens on the tropospheric oxidative capacity. In the troposphere, the distribution of brominated compounds is more variable and significant uncertainties remain in the chemical processes governing the sources and sinks of reactive bromine compounds. In this study, we use GEOS-Chem simulated stratospheric columns of BrO to separate the tropospheric signal of BrO from the OMI total column measurements. The resulting tropospheric BrO columns are used to identify seasonal and regional anomalies in tropospheric BrO not currently represented in GEOS-Chem. In particular, periods of elevated tropospheric BrO during polar spring are observable by OMI, and past studies have connected these so-called "bromine explosion" events to near complete removal of surface ozone. Due to significant uncertainties in the springtime polar source of reactive bromine, many global models, including GEOS-Chem, do not simulate these tropospheric ozone depletion events. Consequently, OMI-based tropospheric columns of BrO are useful tool for investigating the impact of bromine explosion events on tropospheric ozone depletion episodes as well as background air quality.

Wales, Pamela↗
NASA NTRS2019

Anthropogenic Control over Wintertime Oxidation of Atmospheric Pollutants

Anthropogenic air pollutants such as nitrogen oxides (NO(x) = NO + NO(2)), sulfur dioxide (SO(2)), and volatile organic compounds (VOC), among others, are emitted to the atmosphere throughout the year from energy production and use, transportation, and agriculture. These primary pollutants lead to the formation of secondary pollutants such as fine particulate matter (PM(2.5)) and ozone (O(3)) and perturbations to the abundance and lifetimes of short-lived greenhouse gases. Free radical oxidation reactions driven by solar radiation govern the atmospheric lifetimes and transformations of most primary pollutants and thus their spatial distributions. During winter in the mid and high latitudes, where a large fraction of atmospheric pollutants are emitted globally, such photochemical oxidation is significantly slower. Using observations from a highly instrumented aircraft, we show that multi-phase reactions between gas-phase NO(x) reservoirs and aerosol particles, as well as VOC emissions from anthropogenic activities, lead to a suite of atypical radical precursors dominating the oxidizing capacity in polluted winter air, and thus, the distribution and fate of primary pollutants on a regional to global scale.

Haskins, J. D.↗
NASA NTRS2021

Formaldehyde evolution in U.S. wildfire plumes during FIREX-AQ

Formaldehyde (HCHO) is one of the most abundant non-methane volatile organic compounds (VOCs) emitted by fires. HCHO also undergoes chemical production and loss as a fire plume ages, and it can be an important oxidant precursor. In this study, we disentangle the processes controlling HCHO by examining its evolution in wildfire plumes sampled by the NASA DC-8 during the FIREX-AQ field campaign. In nine of the twelve analyzed plumes, dilution-normalized HCHO increases with physical age (range 1 – 6 h). The balance of HCHO loss (mainly via photolysis) and production (via OH-initiated VOC oxidation) seems to control the sign and magnitude of this trend. Plume-average OH concentrations, calculated from VOC decays, range from –0.5 (± 0.5) × 10 6 to 5.3 (±0.7) × 10 6 cm -3 . The production and loss rates of dilution-normalized HCHO seem to decrease with plume age. Plume-to-plume variability in dilution-normalized secondary HCHO production correlates with OH abundance rather than normalized OH reactivity, suggesting that OH is the main driver of fire-to-fire variability in HCHO secondary production. Analysis suggests an effective HCHO yield of 0.33 (± 0.05) per VOC molecule oxidized for the 12 wildfire plumes. This finding can help connect space-based HCHO observations to the oxidizing capacity of the atmosphere and to VOC emissions.

Air quality↗
NASA NTRS2024

Future CH4 Budgets as Modelled By A Fully Coupled Earth System Model Using Prescribed GHG Concentrations vs. Interactive CH4 Sources and Sinks

We have used the NASA Goddard Institute for Space Studies (GISS) Earth system model GISS-E2.1 to study the future budgets and trends of global and regional CH4 under different emission scenarios. GISS-E2.1 is one of the few ESMs that can be driven by anthropogenic CH4 emissions, as well as interactive natural sources such as wetlands, and can simulate the tropospheric CH4 chemistry. In frame of the recent short-lived climate forcers (SLCFs) assessment by the Arctic Monitoring and Assessment Programme (AMAP), we used the GISS-E2.1 model with prescribed long-lived greenhouse gas (GHG) concentrations. In the present study, we have supplemented these simulations using the interactive CH4 sources and sinks in order to quantify the model performance and the sensitivity to CH4 sources and sinks. We have used the Current Legislation (CLE) and the Maximum Feasible Reduction (MFR) emission scenarios from the Eclipse V6b emission database to simulate the future chemical composition and climate impacts from 2015 to 2050. We have also simulated 1995-2014 in order to evaluate the model performance following the AMAP-SLCF protocol. The prescribed GHG version underestimates the Global Atmospheric Watch (GAW) surface CH4 observations during the period between 1995 and 2023 by 1% [-8.4%-2.0%], with a correlation (r) of 0.71 [-0.41 0.99]. The largest underestimations are over the continental emission regions such as North America, Europe, and Asia, while biases are smallest over oceans. On the other hand, the simulation with interactive sources and sinks underestimates the GAW observations more than the prescribed simulation, by 18.5% [-25% -10.4%], with a lower r of 0.36 [-0.82 0.93]. Opposite to the prescribed simulation, the biases are largest over oceans and smaller over the continents, however they are still larger over land than the prescribed simulation. The interactive simulation, with large sources virtually over land and strong sink over oceans, has a land/ocean ratio larger than 1 while the prescribed simulation has this ratio equal to 1 as it distributes the global prescribed CH4 concentration equally in longitude over a given latitude. This clearly shows that the interactive sources and sinks should be represented in models in order to realistically simulate the chemical composition and the oxidative capacity of the atmosphere. As expected, the MFR scenario simulates lower global surface CH4 concentrations and burdens compared to the CLE scenario, however in both cases, global surface CH4 and burden continue to increase through 2050 compared to present day. In the CLE scenario, increases are largest over the equatorial belt, in particular over India and East China, while the MFR scenario shows increases over the whole Southern Hemisphere, however much smaller compared to CLE. Finally, the interactive simulation shows that the chemical CH4 sink increases in the CLE scenario, while it slightly decreases in the MFR, leading to a larger CH4 lifetime in the MFR scenario compared to in the CLE scenario.

CH4↗
NASA NTRSDate not supplied

Tropical Tropospheric Ozone Trends (1990 to 2022): A Re-evaluation Based on SHADOZ and IAGOS Profiles and TOMS/OMI Columns

Changes in tropical tropospheric ozone (TTO) are of importance because this region spans roughly a third of the Earth and portions of it are experiencing variability in trends of ozone precursors (CO, NO x , CH 4 and nonmethane hydrocarbons) associated with economic growth and fires. In addition to ozone changes affecting radiative forcing, tropical ozone is an important source of the OH radical and thus, the oxidizing capacity of the planet (Thompson, 1992). Recent studies examining TTO trends satellite and in-situ observations over the past ~25 years include: Thompson et al., JGR, 2021; Gaudel et al., ACP, 2023; Stauffer et al., ACP, 2023. The results show considerable regional and seasonal variability in TTO trends and sensitivity to data selection, frequency, and statistical method used. The satellite data vary most widely in method, time period and reliability. Here we revisit trends for the 1990-2022 period with the best-characterized buv-based satellite products that span that period (derived from TOMS and OMI, Ziemke et al., 2019). The satellite-based trends are compared to trends based on in-situ data from the Southern Hemisphere Additional Ozonesondes (SHADOZ) network (1998-2022), measurements from selected pre-SHADOZ and IAGOS commercial aircraft data (Gaudel et al., 2023). Among sensitivities examined are the dependence of ozone trends on start and end years, impacts of ENSO events and the COVID-19 perturbation to emissions. Two statistical methods are used, quantile regression (QR) and multiple linear regression (MLR). Trends of total TTO, ozone segments in the boundary layer (to ~700 hPa), and free troposphere (700-300 hPa) are compared.

ozone, OMI, tropospheric ozone, SHADOZ↗
NASA NTRS2025

Validation of Formaldehyde Products From Three Satellite Retrievals (OMI SAO, OMPS-NPP SAO, and OMI BIRA) in the Marine Atmosphere With Four Seasons of Atom Aircraft Observations

Formaldehyde (HCHO) in the atmosphere is an intermediate product from the oxidation of methane and non-methane volatile organic compounds. In remote marine regions, HCHO variability is closely related to atmospheric oxidation capacity and modeled HCHO in these regions is usually added as a global satellite HCHO background. Thus, it is important to understand and validate the levels of satellite HCHO over the remote oceans. Here we intercompare three satellite retrievals of total HCHO columns (OMI-SAO (v004), OMPS-NPP SAO, and OMI BIRA) and validate them against in situ observations from the NASA Atmospheric Tomography Mission (ATom) mission. All retrievals are correlated with ATom integrated columns over remote oceans, with OMI SAO (v004) showing the best agreement. This is also reflected in the mean bias (MB) for OMI SAO (-0.73±0.87) x 10 15 molec cm -2 , OMPS SAO (-0.76±0.88) x 10 15 molec cm -2 , and OMI BIRA (-1.40±1.11) x 10 15 molec cm -2 . We recommend the OMI-SAO (v004) retrieval for remote ocean atmosphere studies. Three satellite HCHO retrievals and in situ ATom columns all generally captured the spatial and seasonal distributions of HCHO in the remote ocean atmosphere. Retrieval bias varies by latitude and season, but a persistent low bias is found in all products at high latitudes and the general low bias is most severe for the OMI BIRA product. Examination of retrieval components reveals slant column corrections have a larger impact on the retrievals over remote marine regions while AMFs play a smaller role. This study informs that the potential latitude-dependent biases in the retrievals require further investigation for improvement and should be considered when using marine HCHO satellite data, and vertical profiles from in situ instruments are crucial for validating satellite retrievals.

Atom↗
DOE OSTI2022

Preparation of: I. intercalative metal oxide/conductive polymer composites as electrode materials for rechargeable batteries; II. sodium rich manganese oxide hydrate with capacity for aqueous Na-ion electrochemical energy storage

The present invention is directed at intercalative metal oxide/conductive polymer composites suitable for use as electrode materials for rechargeable batteries. The composites can be prepared by agitation of the metal oxide and the conductive polymer in aqueous media. The present invention is also directed at a sodium rich layered manganese oxide hydrate prepared by annealing manganese (II, III) oxide and sodium hydroxide. The sodium rich manganese (III, IV) oxide so formed indicates an enhanced capacity for Na-ion storage suitable for the use of electrode materials for aqueous energy storage.

Xiaowei, Teng↗
DOE OSTI2025

Interlayer pillaring influences the octahedral tilting and electrochemical capacity of tungsten oxides

One strategy to tune the electrochemical properties of layered inorganic materials for energy storage and conversion is to introduce molecular organic pillars. We investigated how pillaring tungsten oxides with alkylammonium cations influences their physical and electrochemical properties relative to the non-pillared host. While the presence of alkylammonium increased the interlayer spacing, we found that the electrochemical capacity of the materials decreased in non-aqueous electrolytes. In aqueous acidic electrolytes, replacement of the interlayer alkylammonium pillars with water molecules led to the recovery of the electrochemical capacity. We rationalize these results based on the influence of interlayer pillars on the degree of octahedral tilting within the inorganic tungsten oxide layers. The presence of alkylammonium in the interlayer leads to an increase in octahedral tilting relative to interlayer water. In turn, this leads to an increase in the band gap and corresponding decrease in the electrochemical capacity. Our findings emphasize the correlation between the chemical nature of the interlayer molecular pillars and the electronic structure, which in turn affects the electrochemical capacity.

36 MATERIALS SCIENCE↗
DOE OSTI2023

Heat capacity of microgram oxide samples by fast scanning calorimetry

Quantitative scanning calorimetry on microgram-sized samples opens a broad, new range of opportunities for studying the thermodynamic properties of quantity-limited materials, including those produced under extreme conditions or found as rare accessory minerals in nature. We calibrated the Mettler Toledo Flash DSC 2+ calorimeter to obtain quantitative heat capacities in the range 200–350 °C, using samples weighing between 2 and 11.5 μg. Our technique is applied to a new set of oxide materials to which it has never been used before, without the need for melting, glass transitions, or phase transformations. Heat capacity data were obtained for silica in the high pressure stishovite (rutile) structure, dense post-stishovite glass, standard fused quartz, and for TiO2 rutile. These heat capacities agree within 5%–15% with the literature values reported for rutile, stishovite, and fused SiO2 glass. The heat capacity of post-stishovite glass, made by heating stishovite to 1000 °C, is a newly reported value. After accurate calibrations, measured heat capacities were then used to calculate masses for samples in the microgram range, a substantial improvement over measurement in conventional microbalances, which have uncertainties approaching 50%–100% for such small samples. Since the typical uncertainty of heat capacities measured on 10–100 mg samples in conventional differential scanning calorimetry is typically 7% (1%–5% with careful work), flash differential scanning calorimetry, using samples a factor of 1000 smaller, increases the uncertainty of heat capacity measurements by a factor of <3, opening the door for meaningful measurements on ultra-small, high-pressure samples and other quantity-limited materials.

Instruments & Instrumentation↗
DOE OSTI2021

Lanthanum induced lattice strain improves hydrogen sulfide capacities of copper oxide adsorbents

This work probes the effects of La on reactions involving CuO sorbents and H 2 S in gaseous streams. La-CuO sorbents with nominal La/Cu atomic ratios of 1:2 achieved higher capacities (27 and 36 g H 2 S per 100 g sorbent) compared to CuO sorbents (25 g H 2 S per 100 g sorbent). Here, comparison of the La-CuO sorbents using energy dispersive x-ray spectroscopy and La L 3 -edge XAS suggested that increased capacity resulted from more uniform dispersion of La within the CuO phase (3.3 wt.% vs. 1.0 wt.% La). X-Ray absorption near edge structure analysis suggested more electron-rich Cu species in La-CuO samples, while extended X-ray absorption fine structure modeling showed an increase in single-scattering path lengths for neighboring and near-neighbor atoms. These changes suggest that La induces strain in the Cu-O lattice, thereby increasing H 2 S capacity by reducing energy barriers associated with surface reactions between oxygen atoms and adsorbed H 2 S molecules.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2023

Packaging Capacity Calculation: Pu Oxide Packaging Options with the 2 Quart SAVY Container

This calculation supports programmatic efforts to Dilute and Dispose Pu. Metal is to be oxidized at LANL, then transported to SRS for dilution at SRS. Ultimately, the diluted oxide will be disposed of at the Waste Isolation Pilot Plant (WIPP). Currently 3013 containers are used to package the oxide, which are placed in to 9975 Type B shipping containers. The Oxide Packaging Technology Maturation Plan determined that a transition to the used of 2-qt SAVY containers placed in 9977 would increase efficiency in shipping and handling and increase programmatic flexibility. The 2-quart SAVY container meets DOE M 441.1 and TA-55 Documented Safety Analysis requirements for handling and storage of Pu oxide at LANL.

36 MATERIALS SCIENCE↗
NASA NTRS2023

An Ensemble Neural Network Model for Predicting Rare-Earth Oxide and Silicate Heat Capacities at High Temperature

In this work, a neural network model was developed to predict the constant pressure heat capacity for materials in the rare-earth oxide—silica material space. Several model architectures were trained and tested on heat capacity data generated from first-principles density functional theory calculations. Hyperparameter optimization was performed, and the optimal model was selected for heat capacity predictions. The optimal model architecture was found to have a root-mean-squared error of 5.12 ± 3.37 J/mol-K. The optimal model architecture was then used in a bagging ensemble model trained using the leave-one-group-out method to provide error estimates for model predictions. The out-of-bag score for the ensemble model was 0.997. The predicted heat capacities agree well with the DFT and experimental results and were computed orders of magnitude faster than DFT simulations. Machine learning shows the potential to provide a suitable surrogate model for thermochemical property predictions for candidate environmental barrier coating materials but refining of input material features and model architectures could further improve accuracy for these models.

environmental barrier coatings↗
DOE OSTI2021

Improved photosynthetic capacity and photosystem I oxidation via heterologous metabolism engineering in cyanobacteria

Significance Cyanobacteria have been increasingly explored as a biotechnological platform, although their economic feasibility relies in part on the capacity to maximize their photosynthetic, solar-to-biomass energy conversion efficiency. Here we show that cyanobacterial photosynthetic capacity can be increased by diverting cellular resources toward heterologous, energy-storing metabolic pathways and by reducing electron flow to photoprotective, but energy-dissipating, oxygen reduction reactions. We further show that these heterologous sinks can partially contribute to photosystem I (PSI) oxidation, suggesting an engineering strategy to improve both energy storage capacity and robustness by selective diversion of excess photosynthetic capacity to productive processes.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
NASA NTRS2002

Changes in Neutrophil Functions in Astronauts

Neutrophil functions (phagocytosis, oxidative burst, degranulation) and expression of surface markers involved in these functions were studied in 25 astronauts before and after 4 space shuttle missions. Space flight duration ranged from 5 to 11 days. Blood specimens were obtained 10 days before launch (preflight or L-10), immediately after landing (landing or R+0), and again at 3 days after landing (postflight or R+3). Blood samples were also collected from 9 healthy low-stressed subjects at 3 time points simulating a 10-day shuttle mission. The number of neutrophils increased at landing by 85 percent when compared to the preflight numbers. Neutrophil functions were studied in whole blood using flow cytometric methods. Phagocytosis of E.coli-FITC and oxidative burst capacity of the neutrophils following the 9 to 11 day missions were lower at all three sampling points than the mean values for control subjects. Phagocytosis and oxidative burst capacity of the astronauts was decreased even 10-days before space flight. Mission duration appears to be a factor in phagocytic and oxidative functions. In contrast, following the short-duration (5-days) mission, these functions were unchanged from control values. No consistent changes in degranulation were observed following either short or medium length space missions. The expression of CD16, CD32, CD11a, CD11b, CD11c, L-selectin and CD36 was measured and found to be variable. Specifically, CD16 and CD32 did not correlate with the changes in oxidative burst and phagocytosis. We can conclude from this study that the stresses associated with space flight can alter the important functions of neutrophils.

Kaur, Indreshpal↗
DOE OSTI2023

Proton-regulated alcohol oxidation for high-capacity ketone-based flow battery anolyte

Redox flow batteries have a unique architecture that potentially enables cost-effective long-duration energy storage to address the intermittency introduced by increased renewable integration for the decarbonization of the electric power sector. Targeted molecular engineering has demonstrated electrochemical reversibility in natively redox-inactive ketone molecules in aqueous electrolytes. Yet, the kinetics of fluorenone-based flow batteries continue to be limited by slow alcohol oxidation. We show how strategically designed proton regulators can accelerate alcohol oxidation and thus enhance battery kinetics. Fluorenone-based flow batteries with the organic additive ß-cyclodextrin demonstrate enhanced rate capability, high capacity, and long cycling. This study opens a new avenue to improve the kinetics of aqueous organic flow batteries by modulating the reaction pathway with a homogeneous catalyst.

25 ENERGY STORAGE↗